Hindawi Publishing Corporation

International Journal of Mineralogy

Volume 2014, Article ID 648530, 11 pages
http://dx.doi.org/10.1155/2014/648530

Research Article
X-Ray Diffraction and Vibrational Spectroscopic
Characteristics of Hydroxylclinohumite from Ruby-Bearing
Marbles (Luc Yen District, Vietnam)
V. Hurai,1 M. Wierzbicka-Wieczorek,2 M. Pentrk,3 M. Huraiov,4 R. Thomas,5
A. Swierczewska,6 and J. Luptkov7
1

Geological Institute, Slovak Academy of Sciences, Dubravska cesta 9, 840 05 Bratislava, Slovakia
Mineralogy Department, Institute for Geosciences, Friedrich-Schiller University, 077 45 Jena, Germany
3
Institute of Inorganic Chemistry, Slovak Academy of Sciences, 840 05 Bratislava, Slovakia
4
Department of Mineralogy and Petrology, Comenius University, 842 15 Bratislava, Slovakia
5
Helmholtz Center Geoforschungs Zentrum, 144 73 Potsdam, Germany
6
AGH University of Science and Technology, Faculty of Geology, Geophysics and Environment Protection, 30-059 Krakow, Poland
7
Geological Institute, Slovak Academy of Sciences, 974 01 Banska Bystrica, Slovakia
2

Correspondence should be addressed to V. Hurai; vratislav.hurai@savba.sk

Received 28 June 2013; Accepted 22 October 2013; Published 29 January 2014
Academic Editors: M. Arima, A. I. Becerro, J. Du, and B. Tsikouras
Copyright 2014 V. Hurai et al. This is an open access article distributed under the Creative Commons Attribution License, which
permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
A honey-yellow hydroxylclinohumite from ruby-bearing marbles of the Luc Yen district in northern Vietnam was characterized by
electron microprobe (EPMA), single-crystal X-ray diffraction (XRD), micro-Raman, and Fourier-transform infrared (FTIR) spectroscopy. The studied crystals correspond to nearly ideal clinohumite with the structural formula 4[Mg2 SiO4 ][(Mg,Fe,Ti)(OH,F)2 ]
and roughly equal F and OH proportions. Crystal structure analysis showed Ti substitution for Mg only at the Mg3 site. A Fourierdifference map revealed one hydrogen site associated with ninth oxygen atom. The calculated OH bond distance was shorter than
that in other natural clinohumites. FTIR revealed bands corresponding to combination of OH-stretching with MgOH and/or Fe
OH bending modes, combinations of OH and FeOH vibrations, combination of fundamental bands of the SiOH bonding,
combination of OH and SiOH vibrations, and first (2]OH ) and the second (3]OH ) overtones of the OH-stretching vibration
mode. Two groups of OH-stretching vibration and FTIR absorption bands at 33903420 cm1 and 35603580 cm1 show reversible
temperature-dependent shift. The low-frequency bands absent in pure synthetic hydroxylclinohumites are assigned to OH-planar
defects caused by Ti-for-Mg substitution.

1. Introduction
Humite-group minerals have the general formula n(M 2 SiO4 )
M 1x Tix (OH,F)22x O2x , where stands for Mg, Fe, Mn,
Ca, Zn in decreasing order of abundance, < 0.5 and
numbers from 1 to 4 define norbergite, chondrodite, humite
and clinohumite, respectively [1]. The humite-group minerals
have attracted attention owing to the suspicion of being
volatile carriers in subduction zones and the overlying mantle
wedge. This hypothesis was strengthened by occurrences of
chondrodite and clinohumite in eclogite, garnet peridotite
[25], and kimberlite [6], as well as by the experimentally

proven stability of these minerals at high-PT conditions [7, 8].

In addition, the humite-group minerals are typical of the
carbonates metamorphosed under high pressure and/or temperature [915]. Humite-like defects (OH-bearing monolayers) were discovered in nominally anhydrous mantle olivine
[16, 17] and the assignment of the specific IR absorption bands
in olivines to the clinohumite-like point and planar defects
has been a matter of extensive ongoing research [1820].
In spite of their importance for estimating the amount of
water in the upper mantle, interpretation of the vibrational
and absorption spectra of the humite-group minerals remains
inconclusive, partly due to their complexity and partly due to

International Journal of Mineralogy

Prg
An
Chu

An
1 cm
(a)

1 mm
(b)

Figure 1: (a) Honey-yellow crystals of hydroxylclinohumite (Chu) associated with grey anorthite (An) and green pargasite (Prg) in white
calcite matrix. (b) Aggregate of hydroxylclinohumite crystals isolated after dissolution of calcite matrix in hydrochloric acid.

incomplete, erratic, or even missing chemical and structural

characteristics of the studied samples. For instance, Frost et
al. [21, 22] interchanged sampling sites of clinohumite and Ticlinohumite in two companion papers. Their clinohumite
with 7.35 a.p.f.u. (atoms per formula unit) Mg, 0.5 a.p.f.u.
Ca, and 0.13 a.p.f.u. Fe exhibits deficiency of divalent cations
needed for creating the olivine- and brucite-like layers.
Moreover, an extremely high aluminium content (0.45 a.p.f.u.
Al) cannot be allocated in the clinohumite crystal structure.
Yang and Keppler [20] have shown that structural models
of water dissolution in olivine derived from infrared spectra
at atmospheric conditions may not be fully applicable for
the mantle, because some important OH-absorption bands
disappear at low temperatures. Until recently, only absorption spectra of synthetic Ti- and F-poor clinohumite and
chondrodite have been studied at temperatures up to 600 C
and pressures to 29 kbar [23, 24], whilst similar experiments
with natural minerals are missing. Hence, the main intention
of this work is to fill partially the gaps outlined above by
providing the set of complementary EPMA, XRD, Raman,
and FTIR data on natural clinohumite from Vietnam. An
additional benefit of this contribution results from the fact
that though the Vietnamese gem-quality clinohumite is frequently offered in internet auctions, it has not been hitherto
described in the mineral assemblage of the ruby-bearing
marbles, where it occurs [25]. Hence, Raman and FTIR
records from single crystals presented in this study would
yield the reference basis for a nondestructive identification
of the clinohumite in jewellery. Special attention will be paid
to annealing experiments, which are expected to provide
evidence on the nature of OH-absorption bands in natural
clinohumite applicable also to hydrated olivine.

2. Materials and Methods

2.1. Geological Background. The mineral studied is represented by honey-yellow crystals with rounded corners, up to
5 mm in diameter, associated with grey anorthite and green
pargasite-edenite embedded in calcite matrix (Figure 1). The

hand specimen comes from the Cambrian marble unit of the

Luc Yen mining district in Vietnam, belonging to the most
important sources of high quality gem rubies and sapphires
in Southeast Asia. The mining district is situated along the
north-eastern flank of the Day Nui Con Voi Range in the
Red River Shear Zone [26]. The origin of the ruby and the
associated assemblage is linked to the activity of the Red River
shear zone between 35 and 40 Ma coincidental with the deformation of Asian plate after collision with India (Himalayan
orogeny). Gem ruby deposits originated during retrograde
metamorphic path at temperatures of 620670 C and a 2.6
3.3 kbar pressure in the presence of evaporites, which played a
key-role in their formation [27, 28]. Microscopic and electron
microprobe investigation of thin sections from the studied
sample revealed also graphite, pyrrhotite, chalcopyrite, pyrite,
muscovite, phlogopite, margarite, clinochlore, titanite, rutile,
dolomite, ankerite, spinel, thorianite, fluorapatite, forsterite,
zircon, ruby, and sapphire [29].
2.2. Analytical Methods and Techniques. Chemical composition was determined using a CAMECA SX-100 elec ur,
tron microprobe (State Geological Institute of Dionyz St
Bratislava, Slovakia) in WDS mode and standard operating
conditions: 15 keV accelerating voltage, 20 nA beam current,
510 m beam diameter. Calibration was made using natural
and synthetic minerals (main element line, crystal used,
and detection limit in wt.% in parentheses): Siwollastonite
(K, TAP, 0.02), Clhalite (K, LPET, 0.01), Korthoclase
(K, LPET, 0.01), Cawollastonite (K, LPET, 0.01), Mg
forsterite (K, TAP, 0.02), Fefayalite (K, LLIF, 0.06), Mn
rhodonite (K, LLIF, 0.05), Crchromium (K, LLIF, 0.05),
Ninickel (K, LLIF, 0.08), TiTiO2 (K, LPET, 0.02), and
FLiF (K, LPC0, 0.09). Raw analyses were recalculated
to weight percents of oxides using a standardized PAP
correction [30].
A Nonius Kappa APEX II single-crystal X-ray diffractometer with graphite-monochromated MoK radiation
(Institute of Inorganic and Analytical Chemistry, FriedrichSchiller University, Jena, Germany) was used to collect

International Journal of Mineralogy

intensity data from a single crystal at 120 C. Data were
corrected for Lorentz, polarization effects, and background,
but not for absorption effects [31, 32]. The crystal structure
was refined by full-matrix least-squares techniques on F 2
in the nonstandard space-group setting P21 /b11 (atomic
coordinates and anisotropic displacement parameters for the
non-H-atoms; SHELXL-97 [33]). The atomic coordinates of
clinohumite given by Friedrich et al. [34], excluding the H
atom, served in the starting set for the structure refinement.
Raman spectra were recorded with Horiba Jobin-Yvon
LabRam HR800 spectrometers (Helmholtz Centre GFZ,
Potsdam, Germany, and Geological Institute SAS, Banska
Bystrica, Slovakia) at room temperature and pressure. The
spectrometers with 1800 gr/mm gratings were equipped with
an Olympus optical microscope. Crystals were irradiated
using a 488 nm laser excitation of a Coherent Innova 70C Ar+
laser with a power of 300 mW (about 14 mW on sample) and
with a 633 nm, 17 mW LHX1 CVI Melles Griot He-Ne laser.
A long-working-distance LMPLanFI 100/0.8 objective was
used for focusing the laser beam and collecting the scattered
light. The focused laser spot on the sample was 1 m in
diameter. The spectra were collected at 20 C with a Peltiercooled (70 C) multichannel CCD detector (1024 256
pixels) in two separate regions, at 701100 cm1 and 2600
4000 cm1 . Maximum spectral resolutions corresponded to
0.4 cm1 using the 488 nm laser excitation and 0.3 cm1 for
the 633 nm laser excitation. Positions of the Raman bands
were controlled according to principal plasma lines of the
argon laser and neon glow lamp. The difference between
recommended and measured line positions was less than
0.6 cm1 .
FTIR spectra in the middle infrared (MIR) region (4000
400 cm1 ) were recorded using a Nicolet 6700 spectrometer
equipped with a KBr beam splitter and KBr DTGS detector
at Institute of Inorganic Chemistry, Slovak Academy of
Sciences, Bratislava, Slovakia. The KBr-pressed disc technique (1 mg of sample mixed with 200 mg of KBr) and a
Smart Orbit, high-performance diamond single-bounce ATR
accessory, were used. The KBr discs were heated at 150 C
for 12 hours to minimize the content of adsorbed water.
For each sample, 128 scans with a resolution of 4 cm1
were recorded. For the near infrared (NIR) region (12000
4000 cm1 ), a CaF2 beam splitter, an InGaAs detector, and
a Smart Diffuse Reflectance (DRIFT) accessory were used
to obtain spectra from KBr discs and single clinohumite
crystals. Finally, MIR spectra were obtained from powdered
clinohumite put into the DRIFT accessory equipped with
an environmental chamber purged with nitrogen gas and
heated under controlled temperature up to 900 C. A total of
256 scans with a resolution of 2 cm1 were recorded in this
mode. Spectral treatment was performed using the OMNIC
software package (Nicolet Instruments Corp).
Frequencies of Raman and FTIR bands were obtained by
curve-fitting procedures provided with the Peakfit software,
version 4.12, from the SeaSolve Software Inc., USA. Band
fitting was done using a Gauss-Lorentz area cross-product
function, Savitsky-Golay or FFT smoothing algorithms, and
a minimum number of component bands. The residuals

3
Table 1: Average composition and chemical formula of hydroxylclinohumite from Vietnam.
Oxide
SiO2
TiO2
MgO
FeO
F
O=F
H2 O
Total

wt.%
38.5(1)
0.52(3)
57.6(2)
0.48(2)
2.89(8)
1.22(3)
1.52(3)
100.3(3)

Ion
Si4+
Ti4+
Mg2+
Fe2+
F

Average a.p.f.u.
3.997
0.041
8.911
0.042
0.948

OH

1.052

a.p.f.u.: atoms per formula unit; numbers in parentheses are standard

deviations (1) referred to last decimal digit.

OH=2-F, H2 O content back-calculated from the calculated OH content,

other elements (Na, K, Ca, Al, Mn, Cr, Ni, Ca, and Cl) below detection limits.

method enabled visualisation of hidden peaks. The fitting

was repeated until the convergence was reached at squared
correlations of 2 goodness better than 0.995.

3. Results
3.1. Chemical Composition. EPMA analyses recalculated
on basis of 13 cations and 18 oxygen atoms (Table 1)
document nearly complete occupancy of tetrahedral site
with Si (3.9964.000 a.p.f.u). The surplus titanium (0.038
0.039 a.p.f.u.) over the negligible tetrahedrally coordinated Ti
(max. 0.004 a.p.f.u.) together with the Mg-excess over tetrahedrally coordinated Mg (0.9070.917 a.p.f.u.), plus minor
amounts of Fe (0.0400.043 a.p.f.u.) and Mn (0.002 a.p.f.u.)
sum to 1 atom per formula unit (a.p.f.u.) in the octahedrally
coordinated M-site, thus resulting in the nearly ideal chemical formula 4[Mg2 SiO4 ][(Mg,Fe,Ti)(OH,F)2 ] with = 4
that is diagnostic of clinohumite. Predominance of OH(O)
over F points to hydroxylclinohumite; however, the exact
F/OH ratio remains uncertain due to the unknown content
of oxygen anions, which may reach up to 0.08 a.p.f.u.,
assuming their bonding with octahedrally coordinated Ti [1],
and also due to the matrix effect on the F concentrations
analysed in the silicate mineral using the LiF standard [35].
3.2. Crystal Structure. The hydroxylclinohumite crystal studied exhibited good quality, with no evidence of twinning
or other unusual features. The final structural refinement
yielded R1(F) = 1.98% for 1354 observed reflections and 150
parameters (Table 2). The highest residual electron-density
3 at a distance of
peak in clinohumite corresponds to 0.39 e/A
from the O1,1 site. The deepest hole in the difference
0.81 A
from the Si1 site. The
3 at a distance of 0.68 A
map is 0.28 e/A
final displacement parameters are given in Table 3, whereas
Table 4 contains anisotropic displacement parameters for
all non-H atoms. Finally, selected bond lengths and results
of bond-valence calculations (bond-valence sums, BVS, in
valence units, v.u.) are summarized in Table 5.
The crystal structure of the studied clinohumite consists
of isolated SiO4 tetrahedra and octahedrally coordinated

International Journal of Mineralogy

a

Table 2: Crystal data, data-collection information, and refinement

details.
Crystal data
Formula
Molecular weight
Colour
Crystal system
Space group,
at 153 K
, , (A)

( ) at 153 K
3)
(A
(000), calc (g/cm3 )
(mm1 )
Crystal dimension (mm)
Data Collection
Diffractometer
(K)
(Mo) (A),
Crystal-detector dist. (mm)
Collection mode, 2max ( )
Rotation axis, width ( )
Total no. of frames
Collect. time per degree (s)
, , ranges
Total reflections measured
Unique reflections
Refinement
Refinement method
Weighting coefficients ,
No. of refined parameters
1(), 2(2 )all
Observed refls.
Extinction coefficient
GooF
3)
min , max (/A

(Mg8.95 Ti0.05 )(SiO4 )4 F1.03 OH0.97

624.41
Canary-yellow
Monoclinic
P21 /b, 2
4.7401(9), 10.231(2), 13.644(3)
100.82(3)
649.9(2)
620, 3.19
1.1
0.10 0.09 0.07
NONIUS KAPPA APEX II
0.71069, 153
33.2
sphere, 54.2
, , 1
288
17
6/5, 12/13, 15/17
3546
1426 (int 2.16 %)
Full-matrix least-squares on 2
0.0161, 0.3314
150
1.98%, 4.95%
1354[ > 4( )]
0.0563(18)
1.134
0.282, 0.391

int = [2 2 (mean)]/2 , 1 = || | | ||/| |; 2 =

2

1/2

{[(2 2 ) ]/[(2 ) ]} .
unit cell parameters at 25 C are as follows: = 4.7479(9), = 10.2387(20),
= 13.6480(27), and = 100.89(3) .

= 1/[2 (2 ) + ()2 + ], where = (max(2 , 0) + 2 2)/3.

1/2

GooF = {[(2 2 ) ]/( )}

is number of refined parameters.

, where is number of reflections and

Mg2+ cations (Figure 2). The Mg2+ cations are characterized

by five different octahedral sites: M(1)c and M(2)6 are like
those in olivines and M(1)N , M(2)6 , and M(3) are like those
in humite [36]. The edge-sharing octahedra form zig-zag
chains along the c-axis, separated by Si1- and Si2-centred
tetrahedra. The linkage of SiO4 tetrahedra to Mg25 - and
Mg26 -centred octahedra, which decorate the chain, results in
their distortions. The long bond distances along this chain are
for Mg26 O1,4.
for Mg25 O2,4 and 2.234 A
2.209 A
Previous studies have either found hydrogen atoms in
two different positions [37], at one site [38] or none at
all [36]. Our Fourier-difference map shows only one H

Figure 2: Crystal structure of hydroxylclinohumite from Vietnam

generated by XtalDraw module [60]. Shown is a half of the unit cell
viewed along -axis.

site with the atomic coordinates similar to that described

by Friedrich et al. [34] and Platonov et al. [39]. The site
occupancy of the hydrogen atom was fixed to that of the
respective donor oxygen atom (47.7%). Refinements of the
scattering power of all five Mg sites indicated a Ti-for-Mg
substitution only at the Mg3 site, with 2.4% of the Mg3 site
being occupied by Ti4+ . The substitution previously described
by Kocman and Rucklidge [40] and Fujino and Takeuchi
[38] involves anion replacement of O2 for (F, OH) to
yield the formula: Mg8 Si4 O16 Mg0.95 Ti0.05 (F,OH)1.9 O0.1 . The
replacement of (OH) by F or Mg by Ti stabilizes the crystal
structure [38]. Electron probe analyses show a small amount
of Fe (0.042 a.p.f.u.). It is possible that this small Fe content is
distributed among all five MgO6 octahedra, but this cannot
be supported by the refinement.
Our structural refinement showed the hydroxylclinohumite from Vietnam to exhibit the OH F substitution.
More than 50% of the available oxygen sites are occupied
by fluorine atoms (refined O : F ratio = 0.477(4) : 0.523(4)).
The discrepancy between minimal refined predominance of
fluorine over hydroxide (F1.03 OH0.97 ) compared to the electron microprobe analyses (F0.95 OH1.05 ) could result from
measurement inaccuracy, matrix effect on EPMA analyses of
fluorine [35], and/or minor chemical zonation. Considering
all of these factors, the agreement between the structural and
EPMA data is excellent.
The OH F substitution influences the intra-polyhedral
and
bond distances of Mg3/Ti3O/F (2.0197(10) A
as well as
and Mg25 O/F (2.0572(11) A)
2.0393(10) A)
the inter-polyhedral angle of Mg25 O/FMg3/Ti3 (130.66 ).
Compared to the F-free Ti-clinohumite from Val Malenco

[34], these bond distances are longer, that is, 2.035(2) A

2.059(2) A,
respectively, as expected from
and 2.070(2) A,
a weaker Mg/TiF bond. The mentioned inter-polyhedral
angle is slightly smaller (128.7 ). Friedrich et al. [34]
described other F-bearing Ti-clinohumite from Kuh-i-Lal
(Pamir Mts.), where the O : F ratio is inverse to that in
our sample [0.516 : 0.484], while the intrapolyhedral bond
distances and angle are comparable with those in our sample
and 2.050(2) A,
2.057(2) A
and 129.85 , resp.).
(2.030(2) A

International Journal of Mineralogy

Table 3: Fractional atomic coordinates and equivalent isotropic atomic displacement parameters for (Mg8.95 Ti0.05 )(SiO4 )4 F1.03 OH0.97
hydroxylclinohumite.

0.5
0.49754(8)
0.00935(9)
0.50902(9)
0.49278(9)
0.07336(7)
0.07655(7)
0.73316(19)
0.27828(19)
0.22309(19)
0.22211(19)
0.23638(19)
0.77894(19)
0.72441(19)
0.72798(19)
0.26229(19)
0.090(10)

Atom
Mg1C
Mg1N
Mg25
Mg26
Mg3
Si1
Si2
O1,1
O1,2
O1,3
O1,4
O2,1
O2,2
O2,3
O2,4
F
H

0.0
0.94627(4)
0.14027(4)
0.25031(4)
0.87792(5)
0.06623(3)
0.17671(3)
0.06463(9)
0.41986(9)
0.11231(9)
0.15865(9)
0.32266(9)
0.96858(9)
0.27995(9)
0.22672(9)
0.04631(8)
0.020(5)

equiv
0.00564(15)
0.00572(13)
0.00623(13)
0.00543(13)
0.00673(16)
0.00437(12)
0.00443(12)
0.0061(2)
0.00578(19)
0.0067(2)
0.0067(2)
0.0061(2)
0.0063(2)
0.0066(2)
0.0065(2)
0.0093(2)
0.050

0.5
0.27411(3)
0.17013(3)
0.38821(3)
0.04300(3)
0.38929(3)
0.83517(3)
0.38804(6)
0.38785(6)
0.29332(7)
0.48625(7)
0.16264(6)
0.16240(7)
0.26242(7)
0.07007(7)
0.05580(6)
0.013(4)

According to Fischer and Tillmanns [57].

Fixed in the refinement.

Occupancy: Mg3/Ti3 = Mg0.976(2) Ti0.024(2), O/F = O0.477(4) F0.523(4) , H = H0.477(4) .

Table 4: Anisotropic atomic displacement parameters for (Mg8.95 Ti0.05 )(SiO4 )4 F1.03 OH0.97 hydroxylclinohumite.
Atom
Mg1C
Mg1N
Mg25
Mg26
Mg3
Si1
Si2
O1,1
O1,2
O1,3
O1,4
O2,1
O2,2
O2,3
O2,4
F

11
0.0051(3)
0.0051(2)
0.0064(2)
0.0061(2)
0.0069(3)
0.00355(19)
0.00379(19)
0.0048(4)
0.0059(4)
0.0056(4)
0.0057(4)
0.0047(4)
0.0061(4)
0.0059(4)
0.0061(4)
0.0102(4)

22
0.0070(3)
0.0065(3)
0.0058(2)
0.0047(2)
0.0075(3)
0.00490(19)
0.00483(19)
0.0068(4)
0.0057(4)
0.0082(4)
0.0069(4)
0.0071(4)
0.0058(4)
0.0080(4)
0.0072(4)
0.0078(4)

33
0.0048(3)
0.0048(2)
0.0064(2)
0.0052(2)
0.0052(2)
0.00443(19)
0.00448(19)
0.0063(4)
0.0056(4)
0.0063(4)
0.0068(4)
0.0063(4)
0.0066(4)
0.0063(4)
0.0055(4)
0.0098(4)

23
0.0012(2)
0.00077(19)
0.00124(18)
0.00007(18)
0.00009(17)
0.00031(13)
0.00038(14)
0.0004(3)
0.0008(3)
0.0015(3)
0.0004(3)
0.0008(3)
0.0004(3)
0.0024(3)
0.0003(3)
0.0013(3)

13
0.0007(2)
0.00052(16)
0.00029(16)
0.00007(16)
0.00055(16)
0.00003(12)
0.00002(12)
0.0001(3)
0.0004(3)
0.0003(3)
0.0009(3)
0.0001(3)
0.0002(3)
0.0000(3)
0.0006(3)
0.0025(3)

12
0.0001(2)
0.00049(16)
0.00011(15)
0.00020(15)
0.00045(16)
0.00004(12)
0.00009(12)
0.0001(3)
0.0001(3)
0.0002(3)
0.0003(3)
0.0001(3)
0.0005(3)
0.0004(3)
0.0002(3)
0.0009(3)

Occupancy: Mg3/Ti3 = Mg0.976(2) Ti0.024(2), O/F = O0.477(4) F0.523(4) .

in both SiO4
The average SiO bond length is 1.633 A
tetrahedra. The hydrogen site is associated with the ninth
oxygen atom (labeled O/F here) and occupies about half
(47.7%) of the general position. The OH and H H bond
and 1.018 A
respectively.
distances correspond to 0.99(4) A,
Calculated BVS for the Mg and Si sites are close to
expected values: 2.02 (Mg1C )/1.99, (Mg1N )/1.91, (Mg25 )/1.88,
(Mg26 )/2.08 (Mg3), and 3.90 (Si1)/3.91 (Si2). As expected

from the small Ti content in the Mg3 site, this site shows the
highest calculated BVS (2.08 v.u.) among all five Mg sites. The
relatively low BVS for Mg25 and Mg26 are explained in terms
of long MgO distances of the distorted octahedra. The BVS
values for O bonds from O1,1 to O2,4 are consistent with those
reported by Ferraris et al. [37]. The O/F anion with a BVS
of 1.10 is underbonded, which results from the 55% F-for-O
substitution.

International Journal of Mineralogy

and calculated
Table 5: Selected geometric parameters (A)
bond-valence sums (BVS) for the coordination polyhedra in
(Mg8.95 Ti0.05 )(SiO4 )4 F1.03 OH0.97 hydroxylclinohumite.
Atom1Atom2

Bond length (A)

BVS
0.36

Mg1C O1,2

2.0694(10)

Mg1C O1,2

2.0694(10)

0.36

Mg1C O1,1

2.0908(10)

0.34

Mg1C O1,1

2.0908(10)

0.34

Mg1C O1,4

2.1258(10)

0.31

Mg1C O1,4

2.1258(10)

0.31

2.095

2.02

Mg1N O2,2

2.0700(10)

0.36

Mg1N O1,2

2.0853(10)

0.35

Mg1N O2,1

2.1023(11)

0.33

Mean

Mg1N O1,1

2.1032(11)

0.33

Mg1N O1,3

2.1165(10)

0.32

Mg1N O2,3

2.1345(10)

0.30

2.102

1.99

Mg25 O1,3

2.0284(11)

0.40
0.38

Mean
Mg25 O2,2

2.0543(10)

Mg25 O/F

2.0572(11)

0.35

Mg25 O2,1

2.1731(10)

0.27

Mg25 O2,3

2.1855(11)

0.26

Mg25 O2,4

2.2087(11)

0.25

2.12

1.91

Mg26 O1,2

2.0514(10)

0.38

Mg26 O1,4

2.0549(11)

0.38

Mg26 O2,3

2.0677(11)

0.36

Mg26 O1,1

2.1763(11)

0.27

Mg26 O1,3

2.1954(11)

0.26

Mg26 O1,4

2.2337(11)

0.23

2.130

1.88

Mg3/Ti3O2,4

2.0002(11)

0.44

Mg3/Ti3O/F

2.0197(10)

0.38

Mean

Mean

2.0393(10)

0.37

Mg3/Ti3O2,4

2.1204(11)

0.31

Mg3/Ti3O2,1

2.1239(11)

0.31

Mg3/Ti3O2,2

2.1879(11)

0.26

2.082

2.07

Mg3/Ti3O/F

Mean
Si1O1,1

1.6127(10)

1.03

Si1O1,2

1.6512(10)

0.93

Si1O1,3

1.6347(10)

0.97

Si1O1,4

1.6344(10)

0.97

1.633

3.90

Mean
Si2O2,1

1.6127(10)

1.03

Si2O2,2

1.6426(10)

0.95

Si2O2,3

1.6380(10)

0.96

Si2O2,4

1.6381(10)

0.96

1.633

3.90

Mean

Table 5: Continued.

Bond length (A)

BVS
Hydrogen bond
OH
0.99(4)
O/F O/F
2.976
O/FHO/F
172.49
H O/F
1.992
H H
1.018
BVS (v.u.) for the oxygen atoms: O1,1 = 1.97; O1,2 = 2.02;
O1,3 = 1.95, O1,4 = 1.89; O2,1 = 1.95; O2,2 = 1.95; O2,3 =
1.89; O2,4 = 1.96; O/F = 1.10
Atom1Atom2

BVS are calculated according to the refined occupancy for oxygen [58] and
fluorine atoms ([59]; updated values from http://www.ccp14.ac.uk/ccp/webmirrors/i d brown/).

3.3. Raman and FTIR Spectroscopy. Raw single-crystal

Raman spectra are displayed in Figure 3. The region below
350 cm1 , corresponding to vibrations of MO6 octahedra
[21], contains plethora of weak bands, of which the most
intense ones are located at 187, 307, and 321 cm1 . These bands
occur at any crystal orientation, together with those at 75,
84, and 93 cm1 . Other minor peaks in this region are either
broad, having 1 errors greater than 1-2 cm1 , or they are
strongly polarization-dependent and do not appear at some
crystal orientations.
The region between 400 and 500 cm1 , corresponding
to vibrations of MOH units [7] contains only one weak,
polarization-insensitive band at 431 cm1 . In contrast, strong
vibrations occur between 500 and 700 cm1 , corresponding
to the MO stretching vibrations [41] and asymmetric bending vibrations of (SiO4 )4 tetrahedra [21, 42]. These bands
exhibit a strong polarization effect. The band component
analysis revealed that two small bands at 545 and 586 cm1
which appear at the maximum height of the 608 cm1 band
are doublets, composed of 539, 550, and 577, 590 cm1 bands,
respectively. These doublets are discernible only when the
608 cm1 band is strongly reduced.
The region between 6501100 cm1 contains the most
intense bands, thus yielding the fingerprint pattern for the
humite-group minerals [21]. The bands at 8001000 cm1 are
assigned to symmetric or asymmetric stretching of (SiO4 )4
tetrahedra [24, 42], while those between 700 and 800 cm1
are attributed to a MOH bending [4244]. A band pair
at 650 and 690 cm1 likely associated with FeO lattice
vibrations [45] is missing in our samples. Band component
analysis shows that the broad band at 748 cm1 consists of two
bands centred at 740 and 757 cm1 , while the single band at
786 cm1 occurs at any orientation. The triplet consisting of
832, 845 and 862 cm1 bands is typical of clinohumite, humite
and chondrodite, but small hidden peaks at 810 and 876 cm1
on both flanks of the triplet were revealed only in clinohumite
[21].
The fundamental OH-stretching vibration region exhibits
a doublet around 3400 cm1 and a triplet extending from
3560 to 3580 cm1 . The two well-separated groups of

845 861

2200

3578

2000
1600
1400
1200
1000

3410

876
931
968

Intensity (cnts)

1800

3393

800
600

912

400
200
2600

100 200 300 400 500 600 700 800 900 1000 1100
Raman shift (cm1 )

2800

3000

3200

3400

3600

3800

4000

Raman shift (cm1 )

Chum2
Chum2-90

3560

2400

3570

832

756
786

609
549
590

186
212
233
306
321
348

9000
8500
8000
7500
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
500

110

Intensity (cnts)

International Journal of Mineralogy

Chum2

Chum2-90

(a)

(b)

4000

910

11283
11472

Absorbance (103 )

5074

4438
4514

912

6940
6960

4328

914

4184
4238

970
965
960
955
950
945
940
935
930
925
920
915
910
905
900

4097

Absorbance (103 )

Figure 3: Baseline-corrected raw Raman spectra of hydroxylclinohumite from Vietnam illustrating strong polarization effect on the bands
intensity.

908
906
904
902
900

4400 4800 5200 5600

Wavenumber (cm1 )

6000

6000

(a)

7000

8000
9000
10000
Wavenumber (cm1 )

11000

12000

(b)

Figure 4: Raw DRIFT FTIR spectrum of hydroxylclinohumite powder.

hydroxyl bands are typical of all natural humite-group minerals except for norbergite and also for hydrated olivine [14,
17, 42]. Band component analysis showed two overlapping
bands centred at 3392 and 3412 cm1 for the low-frequency
region, as well as three sharp maxima at 3560, 3570, and
3579 cm1 in the high-frequency bands. All of these bands are
also infrared-active. No Raman-active modes were observed
between 4000 and 5000 cm1 .
In spite of relatively high 2 correlation factors (0.992
0.997) achieved for the whole segment of the Raman spectrum at 33003700 cm1 , the peak fitting leaves a relatively
high number of spots outside the 2 or even 3 probability
levels. Particularly the 3560 and 3570 cm1 bands are obviously skewed to their right sides. Component analysis reveals
that these bands are in fact doublets. The band at 3560 cm1
consists of two components centred at 3559 and 3562 cm1 ,
while that at 3570 cm1 consists of two modes centred at 3569

and 3574 cm1 . The observed number of bands is minimal,

and a greater number of components substantially improve
statistical parameters of deconvolution. For instance, Ye et al.
[45] decomposed the two major 3552 and 3560 cm1 bands in
synthetic hydroxylclinohumites to as much as 5 components.
It is also worth noting that two small but distinct bands at
3500 and 3608 cm1 observed in both synthetic pure Mg- and
Fe-bearing hydroxylclinohumites (ibid.) are missing in the
hydroxylclinohumite from Vietnam.
Near- and mid-FTIR spectra of hydroxylclinohumite
crystals and powder exhibited major bands at 3393, 3415,
3558, 3568, 3577, 4097, 4328, 4438, 4514, and 5074 cm1 and
minor bands near 3528, 3692, 4184 and 4238 cm1 with
little shoulder near 4249 cm1 (Figures 4 and 5). The band
near 4097 cm1 belongs to a combination of OH-stretching
and MgOH bending modes, while that at 4184 cm1 is
attributed to combination of ](OH) and ](MgO) modes

International Journal of Mineralogy

3558
3568
3577

0.7

3528

0.3

3692
3300

3400

3500

3600

3700

Wavenumbers (cm )

Figure 5: Band-component analysis of a DRIFT FTIR spectrum of

hydroxylclinohumite powder in the OH-stretching region.

25 C

Absorbance

0.5

3393
3415

Absorbance

0.9

100 C
200 C
300 C
400 C
500 C

[22]. Minor Fe admixture in the clinohumite structure is

documented by two low-intensity bands near 4238 cm1 and
4249 cm1 caused by FeO vibrations (]OH + FeOH ). The
presence of this minor band demonstrates an isomorphous
substitution of Fe2+ for Mg2+ in the MO6 octahedra of
clinohumite [46]. The sharp and intense band at 4328 cm1
reflects the high Mg content in the structure, comprising
the sum of the OH-stretching and the Mg3OH bending
modes [47]. The vibration near 4438 cm1 together with the
associated shoulder near 4458 cm1 is connected with combinations of OH-stretching vibrations and MgOH and/or
FeOH bending modes [46]. The appearance of the very
high intensive sharp band at 4514 cm1 was attributed to
combination of fundamental bands of the SiOH bonding
[48], while the band near 5074 cm1 probably corresponds
to the combination of OH and SiOH vibrations [49]. The
group of four bands at 6940, 6960, 11283, and 11472 cm1
can be interpreted as the first (2]OH ) and the second (3]OH )
overtones of the OH-stretching vibration mode. The band
component analysis of the FTIR spectrum shows only a
minor peak displacement within the OH-stretching region
compared to that recorded by Raman.
Two groups of low- and high-frequency absorption bands
in the hydroxylclinohumite powder exhibit nonequivalent
movement paths on heating accompanied by band broadening and band intensity decrease (Figure 6). The lowfrequency group II bands around 3400 cm1 tend to move
towards higher frequencies with increasing temperature,
whereas the high-frequency bands of the group I between
3560 and 3580 cm1 move in the opposite direction. The
observed changes are reversible, and the initial and final
spectra taken at room temperature are identical. The total
observed shifts are around +9 cm1 for the group II and as
much as 15 cm1 for the 3550 cm1 band of the group I.

4. Discussion
The inferred unit cell parameters and the refined crystal
structure for the Vietnamese hydroxylclinohumite are comparable to those of holotype specimen [37, 50], synthetic [51]
and other natural clinohumites [34, 36, 39]. The Mg2+ cation
is substituted by Ti4+ , Fe2+ , and minor Mn2+ as is usual for

600 C
700 C
Group II
3300

3350

3400

Group I
3450

3500

3550

3600

800 C
3650

Wavenumbers (cm1 )

Figure 6: Thermal effect on the OH-stretching region in hydroxylclinohumite powder recorded by FTIR.

most clinohumites, for example, [52]. Ti4+ -for-Si substitution

indicated by small Si-deficiency in electron microprobe
analyses, for example, [14], was not confirmed by the crystal
structure analysis of the Vietnamese hydroxylclinohumite.
An interesting relationship between concentrations of
Ti4+ cations and F anions and the Mg25 O2,2 bond length
has been observed in two clinohumites studied by Friedrich
et al. [34]. The Mg25 O2,2 bond length increased with
decreasing fluorine and increasing titanium content. This
relationship was due to substitution of Ti4+ at the Mg3 site,
which resulted in strengthened Mg3O2,2 bonds with a bond
Our clinohumite with 0.05 a.p.f.u. of Ti
length of 2.188(1) A.
and 1.03 a.p.f.u. of F exhibits a shorter Mg25 O2,2 bond cor The refined Ti content (0.05 a.p.f.u.)
responding to 2.054(1) A.
lies within the EPMA error margin (0.045 a.p.f.u). The
average MgO bond lengths are consistent with other Fbearing clinohumites, that confirms previous findings of
their independence on the chemical composition ([37] and
is
references therein). The OH bond distance 0.99(4) A
shorter than that in other clinohumites [34, 38], probably
due to lower temperature of measurement (153 K) and/or the
presence of fluorine anions, which are stronger hydrogen
bond acceptors than O2 .
Of particular interest are the Raman and MIR bands of
the OH-stretching vibration region. Libowitzky [53] revealed
a correlation of OH stretching frequencies with O O and
H O bond lengths. This correlation shows that the OH
stretching frequency increases with increasing d(O O)
bond length. Very strong H-bonds appear in the lowfrequency part (below 1600 cm1 ) with d(O O) values
Wavenumbers between 1600 and 3200 cm1
below 2.50 A.
are assigned
and O O distances between 2.50 and 2.70 A

International Journal of Mineralogy

to strong H-bonds. In contrast, weak H-bonds are characteristically above 3200 cm1 with O . O bond lengths of
Hence, our Raman and FTIR investigations clearly
2.70 A.
classify the H-bonds in the Vietnamese hydroxylclinohumite
as weak. This is, however, controversial with the reversible,
temperature-induced shift of two OH-stretching vibration
regions on heating (Figure 6), which in turn indicates OHgroups engaged in strong H-bonding [54].
The two groups of OH-stretching vibration bands at
33903420 and 35603580 cm1 in the Vietnamese hydroxylclinohumite show similarities with the low- and highfrequency bands in hydrated olivinethe most important
water carrier in the mantle, for example, [18, 20]. The absorption bands at 3395 and 3410 cm1 in natural clinohumites
and chondrodites have been assigned to molecular liquidlike water, silanol groups [14], or hydrogen bonding between
OH groups attached to Mg in M-site [42]. Adopting the
observations of the last authors, the absence of the 3345 cm1
band in Vietnam clinohumite indicates no hydrogen bonding
between OH-groups attached to Si in the M-site. The strong
polarisation effect on the low-energy bands and the reversible
band shifting at various temperatures rule out randomly
distributed aqueous liquid inclusions [17].
The absence of 3400 cm1 bands in the Raman spectra
of chemically pure synthetic hydroxylclinohumite [23, 45]
suggests that the observed low-frequency band group in the
Vietnamese hydroxylclinohumite is associated with impurities, for example, Ti, Fe, F, or undetected Bcommon minor
element in natural humite-group minerals [35]. Considering
nearly ideal chemical formula of the Vietnamese clinohumite,
the substantial boron content can be excluded. Similarly, the
effect of Fe3+ point defects (protons coupled with trivalent
ions) as observed in strongly oxidised Fo90 olivines [18]
cannot account for the low-frequency group II bands due to
low total iron content. This conclusion is in agreement with
the absence of the group II bands in synthetic Fe-bearing
OH-clinohumite [45]. In addition, the effect of fluorine can
be also ruled out because the 3390, 3400 and 3415 cm1
bands occur in both F-rich and F-absent Ti-clinohumites
[55]. The low-frequency group II bands can be also attributed
to water incorporated in OH-planar defects, as described in
natural titanian clinohumites and the olivines containing Ticlinohumite lamellae [18, 56]. The observed shift of the lowfrequency group II bands to higher frequencies on heating
would indicate OH-groups engaged in strong H-bonding,
because thermal expansion leads to increasing OHO distance, weakening the H bonds and shifting the corresponding
band positions to higher frequencies [54]. In contrast, the
shift of the high-frequency group I bands to lower frequencies
in the heated hydroxylclinohumite is reminiscent of that
observed in hydrated olivines. The effect was explained by the
increasing anharmonicity of the OH-bonds involved in the
vacancies on the Mg2+ site [20].

the chemical formula 4[Mg2 SiO4 ][(Mg,Fe,Ti)(OH,F)2 ] and

roughly equal F/OH ratio. Apart from the crystal structure
data, cell parameters, and element substitutions, we describe
a total of 36 Raman and FTIR bands recorded in the spectral
range between 50 and 12000 cm1 and document reversible
opposing temperature-induced shift of two groups of lowand high-frequency OH-stretching vibration bands.

5. Conclusions

[8] R. Stalder and P. Ulmer, Phase relations of a serpentine composition between 5 and 14 GPa: significance of clinohumite and
phase E as water carriers into the transition zone, Contributions
to Mineralogy and Petrology, vol. 140, no. 6, pp. 670679, 2001.

We provide complete chemical, structural, and spectroscopic

characteristics of hydroxylclinohumite from Vietnam, with

Conflict of Interests
The authors declare that there is no conflict of interests
regarding the publication of this paper.

Acknowledgments
The authors are grateful to Helmar Gorls for help with
single-crystal data collection, to Gerald Giester and Uwe
Kolitsch for helpful comments, and to N. Q. Cuong for
geological location of the samples. Establishment of Raman
and X-ray Laboratories was supported by the European
Regional Development Fund under project of the Centre of
Excellence for Integrated Research of the Earths Geosphere
(ITMS-26220120064). Establishment of FTIR Laboratory was
supported by the APVV project Solipha (0033/07). The paper
benefited from critical reviews of five anonymous reviewers.

References
[1] J. N. Jones, P. H. Ribbe, and G. V. Gibbs, Crystal chemistry of
the humite minerals, The American Mineralogist, vol. 54, no.
3-4, pp. 391411, 1969.
[2] B. W. Evans and V. Trommsdorff, Fluorine hydroxyl titanian
clinohumite in Alpine recrystallized garnet peridotite: compositional controls and petrologic significance, The American
Journal of Science, vol. 283, pp. 355369, 1983.
[3] A. I. Okay, Sapphirine and Ti-clinohumite in ultra-highpressure garnet-pyroxenite and eclogite from Dabie Shan,
China, Contributions to Mineralogy and Petrology, vol. 116, no.
1-2, pp. 145155, 1994.
[4] R. Y. Zhang, J. G. Liou, and B. L. Cong, Talc-, magnesiteand Ti-clinohumite-bearing ultrahigh-pressure meta-mafic and
ultramafic complex in the Dabie mountains, China, Journal of
Petrology, vol. 36, no. 4, pp. 10111037, 1995.
[5] I. Katayama, A. Muko, T. Iizuka et al., Dating of zircon from Ticlinohumite-bearing garnet peridotite: implication for timing
of mantle metasomatism, Geology, vol. 31, no. 8, pp. 713716,
2003.
[6] K.-I. Aoki, K. Fujino, and M. Akaogi, Titanochondrodite and
titanoclinohumite derived from the upper mantle in the Buell
Park Kimberlite, Arizona, USA, Contributions to Mineralogy
and Petrology, vol. 56, no. 3, pp. 243253, 1976.
[7] M. Akaogi and S.-I. Akimoto, Infrared spectra of high-pressure
hydrous silicates in the system MgO-SiO2 -H2 O, Physics and
Chemistry of Minerals, vol. 13, no. 3, pp. 161164, 1986.

10
[9] C. Bhattacharyya, Clinohumite marble from Vemali, Srikakulam District, Andhra Pradesh, India, Mineralogical Magazine,
vol. 39, pp. 727729, 1974.
[10] J. M. Rice, Phase equilibria involving humite minerals in
impure dolomitic limestones. Part I: Calculated stability of
clinohumite, Contributions to Mineralogy and Petrology, vol. 71,
no. 3, pp. 219235, 1980.
[11] K. Bucher-Nurminen, On the mechanism of contact aureole
formation in dolomitic country rock by the Adamello intrusion
(northern Italy), The American Mineralogist, vol. 67, no. 11-12,
pp. 11011117, 1982.
[12] K. Ehlers and G. Hoinkes, Titanian chondrodite and cli
nohumite in marbles from the Otztal
crystalline basement,
Mineralogy and Petrology, vol. 36, no. 1, pp. 1325, 1987.
[13] R. Giere, Titanian clinohumite and geikielite in marbles from
the Bergell contact aureole, Contributions to Mineralogy and
Petrology, vol. 96, no. 4, pp. 496502, 1987.
[14] M. Satish-Kumar and N. Niimi, Fluorine-rich clinohumite
from Ambasamudram marbles, southern India: mineralogical
and preliminary FTIR spectroscopic characterization, Mineralogical Magazine, vol. 62, no. 4, pp. 509519, 1998.

[15] R. Copjakov
a, S. Vrana, S. Houzar et al., Zirkonolit, baddeleyit
a geikielit v klinohumit-spinel-forsteritovych mramorech z

okol Horazdovic a Prachatic, jihozapadn Cechy,

Acta Musei
Moraviae Scientiae Geologicae, vol. 93, pp. 3751, 2008.
[16] M. Kitamura, S. Kondoh, N. Morimoto, G. H. Miller, G. R.
Rossman, and A. Putnis, Planar OH-bearing defects in mantle
olivine, Nature, vol. 328, no. 6126, pp. 143145, 1988.
[17] S. S. Matsyuk and K. Langer, Hydroxyl in olivines from mantle
xenoliths in kimberlites of the Siberian platform, Contributions
to Mineralogy and Petrology, vol. 147, no. 4, pp. 413437, 2004.
[18] A. J. Berry, J. Hermann, H. S. C. ONeill, and G. J. Foran,
Fingerprinting the water site in mantle olivine, Geology, vol.
33, no. 11, pp. 869872, 2005.
[19] E. Balan, J. Ingrin, S. Delattre, I. Kovacs, and M. Blanchard,
Theoretical infrared spectrum of OH-defects in forsterite,
European Journal of Mineralogy, vol. 23, no. 3, pp. 285292, 2011.
[20] X.-Z. Yang and H. Keppler, In-situ infrared spectra of OH in
olivine to 1100 C, The American Mineralogist, vol. 96, no. 2-3,
pp. 451454, 2011.
[21] R. L. Frost, S. J. Palmer, J. M. Bouzaid, and B. J. Reddy, A Raman
spectroscopic study of humite minerals, Journal of Raman
Spectroscopy, vol. 38, no. 1, pp. 6877, 2007.
[22] R. L. Frost, S. J. Palmer, and B. J. Reddy, Near-infrared and
mid-IR spectroscopy of selected humite minerals, Vibrational
Spectroscopy, vol. 44, no. 1, pp. 154161, 2007.
[23] C.-C. Lin, L. G. Liu, T. P. Mernagh, and T. Irifune, Raman spectroscopic study of hydroxyl-clinohumite at various pressures
and temperatures, Physics and Chemistry of Minerals, vol. 27,
no. 5, pp. 320331, 2000.
[24] Z. Liu, G. A. Lager, R. J. Hemley, and N. L. Ross, Synchrotron
infrared spectroscopy of OH-chondrodite and OH-clinohumite
at high pressure, The American Mineralogist, vol. 88, no. 10, pp.
14121415, 2003.
[25] V. Garnier, G. Giuliani, D. Ohnenstetter et al., Marble-hosted
ruby deposits from Central and Southeast Asia: towards a new
genetic model, Ore Geology Reviews, vol. 34, no. 1-2, pp. 169
191, 2008.
[26] L. T. T. Huong, T. Hager, W. Hofmeister et al., Gemstones from
Vietnam: an update, Gems and Gemology, vol. 48, pp. 158176,
2012.

International Journal of Mineralogy

[27] V. Garnier, G. Giuliani, H. Maluski et al., Ar-Ar ages in
phlogopites from marble-hosted ruby deposits in northern
Vietnam: evidence for Cenozoic ruby formation, Chemical
Geology, vol. 188, no. 1-2, pp. 3349, 2002.
[28] G. Giuliani, J. Dubessy, D. Banks et al., CO2 -H2 S-COS-S8 AlO(OH)-bearing fluid inclusions in ruby from marble-hosted
deposits in Luc Yen area, North Vietnam, Chemical Geology,
vol. 194, no. 13, pp. 167185, 2003.
Sliacka, Genesis of ruby from Vietnam [M.S. thesis], Comenius
[29] S.
University, Bratislava, Slovakia, 2009.
[30] J. L. Pouchou and F. Pichoir, Un nouveau mod`ele de calcul
pour la microanalyse quantitative par spectrometrie de rayons
X. Partie II: application a` lanalyse dechantillons heterog`enes en
profondeur, Recherche Aerospatiale, vol. 5, pp. 349367, 1984.
[31] COLLECT, Data Collection Software, Nonius B.V., Netherlands, 1998.
[32] Z. Otwinowski, D. Borek, W. Majewski, and W. Minor, Multiparametric scaling of diffraction intensities, Acta Crystallographica A, vol. 59, no. 3, pp. 228234, 2003.
[33] G. M. Sheldrick, A short history of SHELX, Acta Crystallographica A, vol. 64, no. 1, pp. 112122, 2007.
[34] A. Friedrich, G. A. Lager, M. Kunz, B. C. Chakoumakos, J.
R. Smyth, and A. J. Schultz, Temperature-dependent singlecrystal neutron diffraction study of natural chondrodite and
clinohumites, The American Mineralogist, vol. 86, no. 9, pp.
981989, 2001.
[35] L. Ottolini, F. Camara, and S. Bigi, An investigation of matrix
effects in the analysis of fluorine in humite-group minerals by
EMPA, SIMS, and SREF, The American Mineralogist, vol. 85, no.
1, pp. 89102, 2000.
[36] K. Robinson, G. V. Gibbs, and P. H. Ribbe, The crystal
structures of the humite minerals. IV. Clinohumite and titanoclinohumite, The American Mineralogist, vol. 58, pp. 4349,
1973.
[37] G. Ferraris, M. Prencipe, E. V. Sokolova, V. M. Gekimyants, and
E. M. Spiridonov, Hydroxylclinohumite, a new member of the
humite group: twinning, crystal structure and crystal chemistry
of the clinohumite subgroup, Zeitschrift fur Kristallographie,
vol. 215, no. 3, pp. 169173, 2000.
[38] K. Fujino and Y. Takeuchi, Crystal chemistry of titanian
chondrodite and titanian clinohumite of high-pressure origin,
The American Mineralogist, vol. 63, pp. 535543, 1978.
[39] A. N. Platonov, K. Langer, M. Wildner, E. V. Polshin, and S.
S. Matsyuk, The crystal chemistry of the humite minerals:
spectroscopic studies and structure refinement of an unusual
iron-rich clinohumite, Zeitschrift fur Kristallographie, vol. 216,
no. 3, pp. 154164, 2001.
[40] V. Kocman and J. Rucklidge, The crystal structure of a
titaniferous clinohumite, Canadian Mineralogist, vol. 12, pp.
3945, 1973.
[41] S. Palmer, B. Jagannadha Reddy, and R. L. Frost, Application
of UV-Vis, near-infrared and mid-infrared spectroscopy to the
study of Mn-bearing humites, Polyhedron, vol. 26, no. 2, pp.
524533, 2007.
[42] P. S. R. Prasad and L. P. Sarma, A near-infrared spectroscopic
study of hydroxyl in natural chondrodite, The American Mineralogist, vol. 89, no. 7, pp. 10561060, 2004.
[43] Q. Williams, A vibrational spectroscopic study of hydrogen in
high pressure mineral assemblages, in High-Pressure Research:
Application To Earth and Planetary Sciences , Y. Syono and M.
H. Manghnani, Eds., pp. 289296, Terra Scientific Publishing,
Tokyo, Japan, 1992.

International Journal of Mineralogy

[44] H. Cynn, A. M. Hofmeister, P. C. Burnley, and A. Navrotsky,
Thermodynamic properties and hydrogen speciation from
vibrational spectra of dense hydrous magnesium silicates,
Physics and Chemistry of Minerals, vol. 23, no. 6, pp. 361376,
1996.
[45] Y. Ye, J. R. Smyth, S. D. Jacobsen et al., Crystal chemistry, thermal expansion, and Raman spectra of hydroxyl-clinohumite:
implications for water in Earths interior, Contributions to
Mineralogy and Petrology, vol. 165, pp. 563574, 2013.
[46] R. N. Clark, T. King, M. Klefwa et al., High spectral resolution
reflectance spectroscopy of minerals, Geophysical Research, vol.
B95, pp. 1265312680, 1990.
[47] J. Madejova and P. Komadel, Baseline studies of the clay
minerals society source clays: infrared methods, Clays and Clay
Minerals, vol. 49, no. 5, pp. 410432, 2001.
[48] A. K. Kronenberg, Hydrogen speciation and chemical weakening of quartz, in Silica. Reviews in Mineralogy, P. J. Heaney,
C. T. Prewitt, and G. V. Gibbs, Eds., vol. 29, pp. 123176,
Mineralogical Society of America, Washington, DC, USA, 1994.
[49] Y. Ping, R. J. Kirkpatrick, P. Brent, P. F. McMillan, and X. Cong,
Structure of calcium silicate hydrate (C-S-H): near-, mid-,
and far-infrared spectroscopy, Journal of the American Ceramic
Society, vol. 82, no. 3, pp. 742748, 1999.
[50] V. M. Gekimyants, E. V. Sokolova, E. M. Spiridonov et al.,
Hydroxylclinohumite Mg9 (SiO4 )4 (OH,F)2 : a new mineral of
the humite group, Zapiski Vserossiyskogo Mineralogicheskogo
Obshchestva, vol. 128, pp. 6470, 1999 (Russian).
[51] A. J. Berry and M. James, Refinement of hydrogen positions
in synthetic hydroxyl-clinohumite by powder neutron diffraction, The American Mineralogist, vol. 86, no. 1-2, pp. 181184,
2001.
[52] M. Weiss, Clinohumites: A Field and Experimental Study [Ph.D.
thesis], ETH Zurich, 1997.
[53] E. Libowitzky, Correlation of O-H stretching frequencies and
O-H O hydrogen bond lengths in minerals, in Hydrogen
Bond Research, P. Schuster and P. Wolschann, Eds., pp. 103115,
Springer, Vienna, Austria, 1999.
[54] K. Nakamoto, M. Margoshes, and R. E. Rundle, Stretching
frequencies as a function of distances in hydrogen bonds,
Journal of the American Chemical Society, vol. 77, no. 24, pp.
64806486, 1955.
[55] K. T. Koga, C. J. Garrido, V. Lopez Sanchez et al., Correlation
between compositional and spectral variations in titanian clinohumite, Abstract #V41D-1764, American Geophysical Union,
Fall Meeting, 2006.
[56] J. Hermann, J. D. Fitz Gerald, N. Malaspina, A. J. Berry, and M.
Scambelluri, OH-bearing planar defects in olivine produced
by the breakdown of Ti-rich humite minerals from Dabie Shan
(China), Contributions to Mineralogy and Petrology, vol. 153,
no. 4, pp. 417428, 2007.
[57] R. X. Fischer and E. Tillmanns, The equivalent isotropic
displacement factor, Acta Crystallographica, vol. C44, pp. 775
776, 1988.
[58] N. E. Brese and M. OKeeffe, Bond-valence parameters for
solids, Acta Crystallographica, vol. B47, pp. 192197, 1991.
[59] I. D. Brown, Valence: a program for calculating bond valences,
Journal of Applied Crystallography, vol. 29, pp. 479480, 1996.
[60] R. T. Downs and K. L. Bartelmehs, Computer visualization
of temperature and pressure effects on crystal structures, EOS
Transactions, AGU Spring Meeting Supplement, vol. 77, no. 17, p.
S261, 1996.

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